Dispersing a water-immiscible liquid in an aqueous medium

ABSTRACT

A method of dispersing a water-immiscible liquid in an aqueous medium is disclosed. At least one immiscible liquid is combined with a stable aqueous colloidal solution, formed by a controlled hydrolysis and nucleation reaction and comprising insoluble hydrous oxide particles of one or more selected elements, such solutions being exemplified in U.S. Pat. application Ser. No. 8,022, filed Feb. 2, 1970, now U.S. Pat. No. 3,657,003. The combined liquid source and colloidal solution are then subjected to a dispersive force to (1) fractionate the liquid source to form a plurality of immiscible liquid particles, and (2) disperse the liquid particles within the colloidal solution. Where the liquid source is initially fractionated in a suitable manner, the dispersive force then merely disperses the water-immiscible liquid particles.

United States Patent 1191 1111 3,816,329

Kenney et a]. June 11, 1974 l l DISPERSING A WATER-IMMISCIBLE LIQUID INAN AQUEOUS MEDIUM Primary Examiner-Richard D. Lovering [75] Inventors:John Thomas Kenney, Lawrence Attorney Agent or Flrm J RqsenstockTownship, Mercer County; Frederic Alan Litt, Cranford, both of NJ. [57]ABSTRACT A method of dispersing a water-immiscible liquid in an aqueousmedium is disclosed. At least one immiscible liquid is combined with astable aqueous colloidal so- [73] Assignee: Western Electric Company,

Incorporated, New York, NY.

[22] Filed: May 24, 1972 lutiOn, formed by a controlled hydrolysis andnucleation reaction and comprising insoluble hydrous oxide p 256,550particles of one or more selected elements, such solutions beingexemplified in US. Pat. application Ser. 52 us. c1 252/312, 44/51,117/1355, 8,022, filed 2, 1970, now US 25 252 3 3,657,003. The combinedliquid source and colloidal [5 l] Int. Cl B0lj 13/00 Solution are thensubjected to a dispersive force to (1) [58 Field of Search 252/312, 314fractionate the liquid Source to form a plurality of miscible liquidparticles, and (2) disperse the liquid [56] References Cited particleswithin the colloidal solution. Where the liq- UNITED STATES PATENTS uidsource is initially fractionated in a suitable;manl 44 35 l2/l922 Mona252512 UX ner, the dispersive force then merely disperses the wa-21755I194 7/1956 Volkmann et al. 252/312 x ter'lmm'sclble l'quld parades3.657.003 4/1972 Kenney 252/313 R X 6 Claims, 2 Drawing FiguresBACKGROUND OF THE INVENTION 1. Field of the Invention This inventionrelates to a method of dispersing a water-immiscible liquid in anaqueous medium and more particularly, to a method of dispersingwaterimmiscible liquid organic compounds including hycrocarbons,silicones, etc.

2. Discussion of the Prior Art Emulsions, i.e., dispersions of awater-immiscible liquid in an aqueous medium, have been used forliterally thousands of years. Emulsions are used in cosmetics, foods,polishes, paints, etc. An important application of emulsions is inimpregnating paper, fabric, wood, etc., for ultimate use in electricaland heat equipment.

The appearance, glaze and shape-retaining properties of garments may beimpaired by washing. A process termed finishing or dressing helps torestore garments after washing. The finishing or dressing processescomprise mechanical treatment and processing by chemicals to improve theglaze, shape-retaining properties, crease resistance, smoothness anddrape of the particular material. Additionally, depending on the kind ofmaterial and the purpose for which it is to be used, it can be madeshrinkproof, water repellant, supple, soft or heavy.

Mechanical finishing treatments may consist in mangling, pressing,rolling, milling, shearing, calendering, raising and/or singing.However, before undergoing these treatments, the material is passedthrough liquid baths in which various substances (textile auxiliaries)are applied to the fibres. Suspensions in water of starch, starchderivatives, vegetable gums, glues, gelatins, and mucilages improve theshape-retaining properties after the material has been dried andsmoothed. Waterresistant synthetic substances such as emulsions or dispersions of silicones are employed to waterproof the material.

The various emulsions employed for the abovementioned applications, ofcourse, comprise waterimmiscible liquids suspended or dispersed in anaqueous medium. In order to get the various immiscible liquids dispersedthroughout the aqueous medium, organic surfactants (cationic, non-ionicand anionic) are employed. Eliminating the use of the various organicsurfactants is desirable since the immiscible organic liquids arepartially soluble in the organic surfactants. In the case of silicones,ordinary surfactants are not effective and special surfactants have tobe employed which are expensive. A method whereby organic surfactantscan be eliminated in dispersing water-immiscible liquids in an aqueousmedium is therefore needed.

Within the past few years, pollution from oil spillage in the oceans ofthe world has become a major wildlife threat. When such an oil spillageoccurs, organic surfactants and detergents have been employed todisperse or break up the oil spillage. A problem encountered, however,is that the surfactants and/or detergents may destroy ocean life. Analternative method of dispersing the oil spillage or hydrocarbonaccumulation whereby organic surfactants and detergents are eliminatedis therefore greatly needed.

SUMMARY OF THE INVENTION This invention relates to a method ofdispersing a water-immiscible liquid in an aqueous medium, and moreparticularly, to a method of dispersing waterimmiscible liquid organiccompounds including hydrocarbons, silicones, etc.

Briefly, the inventive technique involves combining a source of theimmiscible liquid with a stable aqueous colloidal solution, formed by ahydrolysis and nucleation reaction, comprising insoluble hydrous oxideparticles of one or more selected elements, the particles having a sizewithin the range of 10A to 10,000A. The hydrolysis reaction includesdissolution of a salt of the selected element in an aqueous medium andmaintenance of the pH of the aqueous medium at a point where noflocculate results. The resultant combination or mixture is thensubjected to a dispersive force to (1) break up or fractionate theliquid source into a plurality of discrete particles which may be ofuniform size and shape, and (2) uniformly disperse the resultantwaterimmiscible liquid particles through the colloidal solution. Wherethe liquid source is initially fractionated in a suitable manner, thedispersive force then merely disperses the water-immiscible liquidparticles. The resultant dispersed immiscible liquid particles will notcoalesce and/or settle for a relatively long period of time.

DESCRIPTION OF THE DRAWING The present invention will be more readilyunderstood by reference to the following drawing taken in conjunctionwith the detailed description, wherein:

FIG. 1 is a cross-sectional view of a discrete source ofawater-immiscible liquid combined with an aqueous stable colloidalsolution contained in a suitable container; and

FIG. 2 is a cross-sectional view of a plurality of waterimmiscibleliquid particles fractionated from the liquid source of FIG. 1 anduniformly dispersed throughout the colloidal solution of FIG. 1 to forma stable dispersed mixture.

DETAILED DESCRIPTION The present invention has been described primarilyin terms of forming and dispersing, in a selected aqueous colloidalsolution, a plurality of discrete, noncoalescing water-immiscible liquidhydrocarbon and silicone particles. However, it will be understood thatsuch description is exemplary only and is for purposes of exposition andnot for purposes of limitation. It will be readily appreciated that theinventive concept described is equally applicable to forming anddispersing in the selected aqueous medium or solution a plurality ofdiscrete, non-coalescing liquid particles of any water insoluble orwater-immiscible liquid, provided, of course, that the selectedimmiscible liquid does not react with the aqueous solution selected.

Referring to FIG. 1, at least one discrete suitable water-insoluble orwater-immiscible liquid source is combined with a suitable stablecolloidal solution 61, contained in a suitable container 62, to form amixture. A suitable liquid source 60 is one comprising a liquid which(I) will not react with the suitable stable colloidal solution 61 withwhich it is destined to be combined, (2) will not dissolve in thecolloidal solution 61 to any appreciable extent, typically being solubleto an extent of less than one weight percent, and, of course, (3) is inthe liquid state at a suitable temperature, i.e., at a temperature atwhich the colloidal solution 61 remains in a stable condition, suchtemperature typically being less than 100 C.

Some typical suitable immiscible liquid sources comprise organic oils,such as fixed oils, essential oils, mineral oils, fuel oils, lubricants(paraffins), silicone oils, creosote, solid organics dissolved insuitable organic solvents, e.g., CCl etc. In this regard, it is again tobe pointed out and stressed that any immiscible liquid unreactive withthe colloidal solution 61 may be employed and dispersed throughout thesolution 61.

The source 60 can be added in any amount ranging from a minimum, whichrepresents a concentration at which the source 60 becomes immiscible orinsoluble in the colloidal solution 61, to 74 percent by volume. It isto be noted that the minimum concentration is dependent on the source60, the colloid solution, the temperature of addition, i.e., all factorswhich are known by one skilled in the art or are easily ascertained. Itis, of course, understood that a suitable container is one which willnot react with either the source 60 or the solution 61 at thetemperature employed. Some typical suitable containers comprise glass,polytetrafluoroethylene, etc. Although the liquid source 60 has beenshown in the form of a layer in FIG. 1, this is for illustrativepurposes only and the liquid source may comprise at least one pool,"droplet, etc. In this regard, it is, of course, understood that if theselected immiscible liquid has a specific gravity greater than that ofthe selected colloidal solution 61, then the source 60 will not befloating" atop the colloidal solution 61, but rather the reverse will betrue.

A suitable colloidal solution 61 includes at least one aqueous wettingsolution revealed in Kenney, US. Pat. Ser. No. 8,022, filed Feb. 2, l970now US. Pat No. 3,657,003, assigned to the assignee hereof andincorporated by reference herein. The wetting solution is generallydescribed as a stable colloidal solution formed by a controlledhydrolysis and nucleation in an aqueous medium wherein thecolloidal-particles 63 (FIG. 1, greatly enlarged for illustrativepurposes only) of the colloidal solution 61, (1) have a size within therange of A to 10,000A, and (2) are an insoluble hydrous oxide of one ormore selected elements. The hydrolysis reaction includes dissolving asalt of the selected element in the aqueous medium and maintaining thepH of the aqueous medium at a point where no flocculate results. Somesuitable elements include Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni,Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, In, Tl, Si, Ge, Sn, Pb, Bi, La, Ce,Th and U. Specifically, the wetting solutions include Examples IA' toXXXIll-L, inclusively, revealed in Kenney.

The resultant mixture comprising the liquid source 60 and the colloidalwetting solution 61 is then subjected to dispersionby means of adispersive force created by .any conventional dispersive device (notshown). Such devices are well known in the art, some typical ones beingconventional stirrers (magnetic, mechanical) and vibrators (sonic,mechanical). Referring to FIGS. 1 and 2, the resultant dispersive forcebreaks up or fractionates the liquid source 60 into a plurality ofdiscrete liquid particles 64 (enlarged for illustrative purposes only).The discrete immiscible liquid particles 64 are uniformly dispersedthroughout the colloidal wetting solution 61 and will not coalesce,i.e., fuse or unite together, while under the influence of thedispersive force. By selecting proper dispersion conditions, includingthe quantum of the dispersive force, the size of the particles 64 can bemaintained uniform. The proper dispersion conditions are well known inthe art or can be easily ascertained experimentally by one skilled inthe art. It is, of course, understood that the water-immiscible liquidsource 60 may be combined with colloidal solution 61 prior to initiatingthe dispersive force or after initiating the dispersive force. It isalso, of course, understood that where the source 60 EXAMPLE I Acolloidal wetting solution was prepared in a suitable container bydissolving one weight percent SnCl2-2H2O in ml. of deionized water. Twoweight percent of SnCl4-5H2O was then dissolved in an resultantsolution. Finally, 1.5 weight percent SnCl2'2I-I O was added anddissolved therein to form a yellow colloidal wetting solution. Fiveweight percent of a commercially obtained, water-immiscible, liquidsilicone oil was added to the wetting solution to form a mixture. Theresultant mixture was stirred at room temperature with a mechanicalstirrer for 5 minutes. A plurality of discrete spherical, non-coalescingsilicone oil particles or droplets of uniform size and shape formed andwere uniformly dispersed throughout the colloidal solution. There was nocoalescence or settling of the resultant dispersion after one week. i

As a measure of stability of the resultant dispersion, the resistance todrop coalescence of the resultant dispersion was compared to that of adispersion obtained using a commercially available surfactant. Theresultant dispersion exhibited a greater resistance resistance to dropcoalescence than that derived from the surfactant.

EXAMPLE II EXAMPLE Ill The procedure of Example I wasrepeated exceptthat a commercially obtained heavy paraffin oil was employed as thewater-immiscible liquid. The resistance to drop coalescence was good.

EXAMPLE IV The procedure of Example III was repeated except that thewetting solution of Example [I was employed. The results of Example IIwere obtained.

It is to be understoood that the above-described embodiments are simplyillustrative of the principles of the invention. Various modificationsand changes may be devised by those skilled in the art which embody theprinciples of the invention and fall within the spirit and scopethereof.

What is claimed is:

l. A method of dispersing a water-immiscible liquid in an aqueous mediumto form a stable aqueous dispersion comprising a plurality of discreteparticles of the liquid, which comprises:

a. combining a discrete source of the immiscible liquid with a stableaqueous colloidal solution, formed by a hydrolysis and nucleationreaction, comprising insoluble hydrous oxide particles of one or moreselected elements, said particles having a size within the range of A to10,000A and said hydrolysis reaction including at least (1) dissolutionof a salt of said selected element in an aqueous medium, and (2)maintenance of the pH of said aque ous medium at a point where noflocculate results; and

b. subjecting said combined liquid source to a dispersive force to (l)fractionate said discrete source to form the plurality of discrete,immiscible liquid particles, and (2) disperse the plurality of discreteparticles within said colloidal solution.

2. The method as defined in claim 1, wherein said one or more elementsis selected from the group consisting of Be, Mg, Ti, Zr, V, Cr, Mo, W,Mn, Fe, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, ln, Tl, Si, Ge, Sn,Pb, Bi, La, Ce, Th, U and mixtures thereof.

3. A method of dispersing a water immiscible liquid in an aqueous mediumto form a stable aqueous dispersion comprising a plurality of discreteparticles of the liquid, which comprises:

a. combining a discrete source of immiscible liquid with a stableaqueous colloidal solution, formed by a hydrolysis and nucleationreaction, comprising insoluble hydrous oxide particles of an elementselected from the group consisting of Sn and Fe, said particles having asize within the range of 10A to 10,000A and said hydrolysis reactionincluding at least (1) dissolution of a salt of said selected element inan aqueous medium, and (2) maintenance of the pH of said aqueous mediumat a point where no flocculate results; and

b. subjecting said combined liquid source to a dispersive force to (l)fractionate said discrete source to form the plurality of discrete,immiscible liquid particles, and (2) disperse the plurality of discreteparticles within said colloidal solution.

4. A method of forming a stable aqueous dispersion comprising aplurality of dispersed water-immiscible liquid particles, whichcomprises:

dispersing the plurality of water-immiscible liquid particles in astable aqueous colloidal solution,

formed by a hydrolysis and nucleation reaction, comprising insolublehydrous oxide particles of one or more selected elements, said particleshaving a size within the range of 10A to 10,000A and said hydrolysisreaction including at least (1) dissolution of a salt of said selectedelements in an aqueous medium, and (2) maintenance of the pH of saidaqueous medium at a point where no flocculate results. 5. The method asdefined in claim 4 wherein said one or more elements is selected fromthe group consisting of Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni,Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, In, Tl, Si, Ge, Sn, Pb, Bi, La, Ce,Th, U and mixtures thereof.

6. A method of forming a stable aqueous dispersion comprising aplurality of dispersed water-immiscible liquid particles, whichcomprises:

dispersing the plurality of water-immiscible liquid particles in astable aqueous colloidal solution, formed by a hydrolysis and nucleationreaction comprising insoluble hydrous oxide particles of an elementselected from the group consisting of Sn and Fe, said particles having asize within the range of lOA to 10,000A and said hydrolysis reactionincluding at least (1) dissolution of a salt of said selected elementsin an aqueous medium, and (2) maintenance of the pH of said aqueousmedium at a point where no flocculate results.

Q UNITED STATES PATENT OFFICE QERHFEQATE 0F CORRECTION Patent Nov5,816,529 W Dated June 11, 197A I an T. Kenney and A0 Litt Inventor(s)It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

In the title section, "Dispersing a Water-Immisoible Liquid in anAqueous Medium" should read -.-Method of Dispersing a Water-ImmisoibleLiquid in an Aqueous Medium--.

I in the specification, oolumnl, line 10, "hycro" should read hydroSigned and sealed this 19th day of November 1974.

(SEAL) 4 Attest:

McCOY M. GIBSON JR. C. MARSHALL DANN Attesting Officer Commissioner ofPatents FORM po'mso I uscoMM-Dc 603764 69 LS/GOVERNMENT PRINTING OFFICE:869- 93 o

2. The method as defined in claim 1, wherein said one or more elementsis selected from the group consisting of Be, Mg, Ti, Zr, V, Cr, Mo, W,Mn, Fe, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, In, Tl, Si, Ge, Sn,Pb, Bi, La, Ce, Th, U and mixtures thereof.
 3. A method of dispersing awater immiscible liquid in an aqueous medium to form a stable aqueousdispersion comprising a plurality of discrete particles of the liquid,which comprises: a. combining a discrete source of immiscible liquidwith a stable aqueous colloidal solution, formed by a hydrolysis andnucleation reaction, comprising insoluble hydrous oxide particles of anelement selected from the group consisting of Sn and Fe, said particleshaving a size within the range of 10A to 10,000A and said hydrolysisreaction including at least (1) dissolution of a salt of said selectedelement in an aqueous medium, and (2) maintenance of the pH of saidaqueous medium at a point where no flocculate results; and b. subjectingsaid combined liquid source to a dispersive force to (1) fractionatesaid discrete source to form the plurality of discrete, immiscibleliquid particles, and (2) disperse the plurality of discrete particleswithin said colloidal solution.
 4. A method of forming a stable aqueousdispersion comprising a plurality of dispersed water-immiscible liquidparticles, which comprises: dispersing the plurality of water-immiscibleliquid particles in a stable aqueous colloidal solution, formed by ahydrolysis and nucleation reaction, comprising insoluble hydrous oxideparticles of one or more selected elements, said particles having a sizewithin the range of 10A to 10,000A and said hydrolysis reactionincluding at least (1) dissolution of a salt of said selected elementsin an aqueous medium, and (2) maintenance of the pH of said aqueousmedium at a point where no flocculate results.
 5. The method as definedin claim 4 wherein said one or more elements is selected from the groupconsisting of Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Pd, Pt, Cu,Ag, Au, Zn, Cd, Hg, Al, In, Tl, Si, Ge, Sn, Pb, Bi, La, Ce, Th, U andmixtures thereof.
 6. A method of forming a stable aqueous dispersioncomprising a plurality of dispersed water-immiscible liquid particles,which comprises: dispersing the plurality of water-immiscible liquidparticles in a stable aqueous colloidal solution, formed by a hydrolysisand nucleation reaction comprising insoluble hydrous oxide particles ofan element selected from the group consisting of Sn and Fe, saidparticles having a size within the range of 10A to 10,000A and saidhydrolysis reaction including at least (1) dissolution of a salt of saidselected elements in an aqueous medium, and (2) maintenance of the pH ofsaid aqueous medium at a point where no flocculate results.